[go: up one dir, main page]

US4061639A - Quinolinesulfonyl compounds - Google Patents

Quinolinesulfonyl compounds Download PDF

Info

Publication number
US4061639A
US4061639A US05/716,747 US71674776A US4061639A US 4061639 A US4061639 A US 4061639A US 71674776 A US71674776 A US 71674776A US 4061639 A US4061639 A US 4061639A
Authority
US
United States
Prior art keywords
quinolinesulfonyl
hydrazine
compounds
bromide
bromine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/716,747
Inventor
Christian T. Goralski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to US05/716,747 priority Critical patent/US4061639A/en
Application granted granted Critical
Publication of US4061639A publication Critical patent/US4061639A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/36Sulfur atoms

Definitions

  • the 5-, 6-, 7- and 8-quinolinesulfonyl chlorides are known; for example, see A. A. Albert et al., J. Chem. Soc., 2384 (1959); R. Ponci et al., Farmco (Pavia), Ed. Sci, 9, 459 (1954) and Chem. Abstr., 49, 11657b (1955); A. Claus et al., J. Prakt, Chem., 40, 447 (1889); and G. Buchmann, et al., J. Prakt. Chem., 16, 152 (1962). Their antimicrobial activity is poor.
  • novel compounds of this invention are quinolinesulfonyl hydrazine and quinolinesulfonyl bromide compounds of the formula ##STR2## wherein R is either a bromine radical (Br--) or a hydrazine radical (H 2 NHH--).
  • novel quinolinesulfonyl hydrazine compounds are herein referred to as "q. hydrazines” and the novel quinolinesulfonyl bromide compounds are herein referred to as "q. bromides”.
  • the novel q. hydrazines consist of
  • the invention's novel compounds are crystalline solids which are of low solubility in water and of moderate solubility in many organic solvents.
  • the q. bromides have been found to have utility in the kill and control of bacterial and fungal organisms.
  • the q. hydrazines have utility as intermediates for making the q. bromides.
  • the q. hydrazines are prepared by slowly adding substantially one molar proportion of the corresponding quinolinesulfonyl chloride (i.e. either 5-, 6-, 7- or 8-quinolinesulfonyl chloride) to substantially two molar proportions of hydrazine at about 5° C to about 15° C.
  • the reaction is advantageously carried out in the presence of an appropriate polar organic solvent, such as, for example, methanol, ethanol or dimethylformamide as reaction medium.
  • an appropriate polar organic solvent such as, for example, methanol, ethanol or dimethylformamide
  • the q. bromides are prepared by slowly adding substantially four molar proportions of bromine to a solution of substantially one molar proportion of the corresponding q. hydrazine (i.e. either 5-, 6-, 7- or 8-q. hydrazine) in a suitable organic solvent, such as chloroform. Said solution should be cooled, prior to the addition of the bromine, by adding crushed ice thereto. After the addition of the bromine is complete and all of the bromine color has disappeared, the layers of the resulting slurry are separated. The organic layer is dried, such as over anhydrous magnesium sulfate. The solvent is removed, advantageously in vacuo, and the product is recrystallized from the resulting residue from an appropriate organic solvent, advantageously hexane.
  • a suitable organic solvent such as chloroform.
  • the above process can be utilized to make three isomers of 8-quinolinesulfonyl bromide, namely 5-, 6- and 7-quinolinesulfonyl bromide, by employing the corresponding quinolinesulfonyl hydrazine.
  • a 500 ml Erlenmeyer flask equipped with a magnetic stirrer and a thermometer is charged with 200 ml of methanol and 3.40 g (0.10 mol) of 95% hydrazine.
  • the solution is cooled to 5° C, and 11.38 g (0.05 mol) of 8-quinolinesulfonyl chloride is added in small portions at a rate such that the reaction temperature does not exceed 15° C.
  • the solution is allowed to warm slowly to room temperature.
  • the precipitating solid is filtered off to give 8.00 g of 8-quinolinesulfonyl hydrazine (C 9 H 9 N 3 O 2 S), m.p. 135°-137° C.
  • the above process can be utilized to make three isomers of 8-quinolinesulfonyl hydrazine, namely 5-, 6- and 7-quinolinesulfonyl hydrazine, by employing the corresponding quinolinesulfonyl chloride.
  • the quinolinesulfonyl bromide compounds of the invention are useful as antimicrobial agents for the control of bacteria and fungi. This is not to suggest that these compounds and mixtures thereof with usual additives are equally effective against all such organisms at the same concentration.
  • these compounds can be employed in an unmodified form or dispersed on a finely divided solid and employed as a dust. Such mixtures can also be dispersed in water with the aid of a surface-active agent and the resulting emulsion employed as a spray.
  • the quinolinesulfonyl bromide compounds can be employed as the active constituents in solvent solutions, oil-in-water or water-in-oil emulsions.
  • compositions containing antimicrobial concentrations are adapted to be formulated as concentrates and subsequently diluted with additional liquid or solid adjuvants to produce the ultimate treating compositions. Good results are obtained when employing compositions containing antimicrobial concentrations and usually from about 100 to about 500 parts by weight of one or more of the compounds per million parts of such compositions.
  • 8-quinolinesulfonyl bromide is dispersed in warm melted nutrient agar which is then poured into petri dishes and allowed to solidify, the quinoline compound being employed in an amount sufficient to provide from 10 to 500 parts by weight thereof per million parts (ppm) of the ultimate agar composition.
  • the surface of the agar is then inoculated with a variety of bacterial and fungal pest organisms, and the inoculated plates are incubated under conditions conducive to bacterial and fungal growth. Similar check plates in which the agar contains no active quinoline or other toxic compound are similarly inoculated and incubated.
  • 8-quinolinesulfonyl bromide gave 100% growth inhibition (kills) and control of the following organisms at the indicated concentrations in parts per million:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Quinolinesulfonyl hydrazine and quinolinesulfonyl bromide compounds of the formula ##STR1## wherein R is either a bromine radical or a hydrazine radical. The quinolinesulfonyl hydrazine compounds are useful as intermediates for making quinolinesulfonyl bromide compounds, the latter being useful as antimicrobials.

Description

BACKGROUND OF THE INVENTION
The 5-, 6-, 7- and 8-quinolinesulfonyl chlorides are known; for example, see A. A. Albert et al., J. Chem. Soc., 2384 (1959); R. Ponci et al., Farmco (Pavia), Ed. Sci, 9, 459 (1954) and Chem. Abstr., 49, 11657b (1955); A. Claus et al., J. Prakt, Chem., 40, 447 (1889); and G. Buchmann, et al., J. Prakt. Chem., 16, 152 (1962). Their antimicrobial activity is poor.
SUMMARY OF THE INVENTION
The novel compounds of this invention are quinolinesulfonyl hydrazine and quinolinesulfonyl bromide compounds of the formula ##STR2## wherein R is either a bromine radical (Br--) or a hydrazine radical (H2 NHH--).
For convenience of description, the novel quinolinesulfonyl hydrazine compounds are herein referred to as "q. hydrazines" and the novel quinolinesulfonyl bromide compounds are herein referred to as "q. bromides".
The novel q. hydrazines consist of
5-quinolinesulfonyl hydrazine;
6-quinolinesulfonyl hydrazine;
7-quinolinesulfonyl hydrazine; and
8-quinolinesulfonyl hydrazine.
The novel q. bromides consist of
5-quinolinesulfonyl bromide;
6-quinolinesulfonyl bromide;
7-quinolinesulfonyl bromide; and
8-quinolinesulfonyl bromide.
The invention's novel compounds are crystalline solids which are of low solubility in water and of moderate solubility in many organic solvents.
The q. bromides have been found to have utility in the kill and control of bacterial and fungal organisms. The q. hydrazines have utility as intermediates for making the q. bromides.
The q. hydrazines are prepared by slowly adding substantially one molar proportion of the corresponding quinolinesulfonyl chloride (i.e. either 5-, 6-, 7- or 8-quinolinesulfonyl chloride) to substantially two molar proportions of hydrazine at about 5° C to about 15° C. The reaction is advantageously carried out in the presence of an appropriate polar organic solvent, such as, for example, methanol, ethanol or dimethylformamide as reaction medium. After the addition of the quinolinesulfonyl chloride is complete, the solution is allowed to slowly warm to room temperature to thereby precipitate the desired product, which is recovered by filtration or other conventional liquids-solids separatory techniques.
The q. bromides are prepared by slowly adding substantially four molar proportions of bromine to a solution of substantially one molar proportion of the corresponding q. hydrazine (i.e. either 5-, 6-, 7- or 8-q. hydrazine) in a suitable organic solvent, such as chloroform. Said solution should be cooled, prior to the addition of the bromine, by adding crushed ice thereto. After the addition of the bromine is complete and all of the bromine color has disappeared, the layers of the resulting slurry are separated. The organic layer is dried, such as over anhydrous magnesium sulfate. The solvent is removed, advantageously in vacuo, and the product is recrystallized from the resulting residue from an appropriate organic solvent, advantageously hexane.
The bromination of arylsulfonyl hydrazines is taught in further detail by Litvinenko et al., Journal of the General Chemistry of the U.S.S.R., Vol. 34, pp. 3780-3782 (1964).
DESCRIPTION OF SOME PREFERRED EMBODIMENTS
The following examples illustrate the present invention and the manner by which it can be practiced but as such should not be construed as limitations upon the overall scope of the same. The product compounds are identified by elemental analysis and/or nuclear magnetic resonance spectroscopy.
EXAMPLE 1 Preparation of 8-Quinolinesulfonyl Bromide
A 500 ml, single-neck flask equipped with a magnetic stirrer is charged with 6.59 g (0.0295 mol) of 8-quinolinesulfonyl hydrazine and 200 ml of chloroform. Crushed ice is added, and the slurry is vigorously stirred. 9.50 g of bromine is added dropwise to the slurry with stirring. After the addition of bromine is complete and all of the bromine color has disappeared, the layers are separated. The chloroform layer is dried over anhydrous magnesium sulfate, and the chloroform is removed in vacuo leaving a pale yellow solid. The solid is slurried with hexane, filtered, and vacuum dried to give 6.00 g (0.221 mol) of 8-quinolinesulfonyl bromide m.p. 142°-144° C.
Anal. -- Calcd. for 8-quinolinesulfonyl bromide (C9 H6 BrNO2 S): C, 39.72; H, 2.22; Br, 29.37; N, 5.14; S, 11.78. Found: C, 39.50; H, 2.30; Br, 28.80 ± 0.2; N, 5.31; S, 12.42.
The above process can be utilized to make three isomers of 8-quinolinesulfonyl bromide, namely 5-, 6- and 7-quinolinesulfonyl bromide, by employing the corresponding quinolinesulfonyl hydrazine.
EXAMPLE 2 Preparation of 8-Quinolinesulfonyl Hydrazine
A 500 ml Erlenmeyer flask equipped with a magnetic stirrer and a thermometer is charged with 200 ml of methanol and 3.40 g (0.10 mol) of 95% hydrazine. The solution is cooled to 5° C, and 11.38 g (0.05 mol) of 8-quinolinesulfonyl chloride is added in small portions at a rate such that the reaction temperature does not exceed 15° C. After the reaction is complete, the solution is allowed to warm slowly to room temperature. The precipitating solid is filtered off to give 8.00 g of 8-quinolinesulfonyl hydrazine (C9 H9 N3 O2 S), m.p. 135°-137° C.
Anal. -- Calcd. for C9 H9 N3 O2 S: C, 48.42; H, 4.06; N, 18.82; S, 14.36. Found: C, 48.40; H, 4.07; N, 18.99; S, 14.30.
The above process can be utilized to make three isomers of 8-quinolinesulfonyl hydrazine, namely 5-, 6- and 7-quinolinesulfonyl hydrazine, by employing the corresponding quinolinesulfonyl chloride.
The quinolinesulfonyl bromide compounds of the invention are useful as antimicrobial agents for the control of bacteria and fungi. This is not to suggest that these compounds and mixtures thereof with usual additives are equally effective against all such organisms at the same concentration. For such uses, these compounds can be employed in an unmodified form or dispersed on a finely divided solid and employed as a dust. Such mixtures can also be dispersed in water with the aid of a surface-active agent and the resulting emulsion employed as a spray. In other procedures, the quinolinesulfonyl bromide compounds can be employed as the active constituents in solvent solutions, oil-in-water or water-in-oil emulsions. The augmented compositions are adapted to be formulated as concentrates and subsequently diluted with additional liquid or solid adjuvants to produce the ultimate treating compositions. Good results are obtained when employing compositions containing antimicrobial concentrations and usually from about 100 to about 500 parts by weight of one or more of the compounds per million parts of such compositions.
In representative activity tests, 8-quinolinesulfonyl bromide is dispersed in warm melted nutrient agar which is then poured into petri dishes and allowed to solidify, the quinoline compound being employed in an amount sufficient to provide from 10 to 500 parts by weight thereof per million parts (ppm) of the ultimate agar composition. The surface of the agar is then inoculated with a variety of bacterial and fungal pest organisms, and the inoculated plates are incubated under conditions conducive to bacterial and fungal growth. Similar check plates in which the agar contains no active quinoline or other toxic compound are similarly inoculated and incubated.
In such operations, 8-quinolinesulfonyl bromide gave 100% growth inhibition (kills) and control of the following organisms at the indicated concentrations in parts per million:
              TABLE 1                                                     
______________________________________                                    
Antimicrobial Activity of                                                 
8-Quinolinesulfonyl Bromide                                               
______________________________________                                    
Organism             Conc. in ppm                                         
______________________________________                                    
S. aureus            500                                                  
E. coli              100                                                  
C. albicans          100                                                  
T. mentagrophytes    100                                                  
A. niger             100                                                  
B. subtilis          100                                                  
A. aerogenes         100                                                  
C. pelliculosa       100                                                  
P. pullulans         100                                                  
S. typhosa           100                                                  
P. Str-10            100                                                  
M. phlei             100                                                  
R. nigricans         100                                                  
C. ips               100                                                  
Trichoderm Sp. Madison P-42                                               
                     100                                                  
______________________________________                                    
In comparative operations, 8-quinolinesulfonyl chloride was tested for antimicrobial activity at 500 ppm using identical agar dilution tests. The following table indicates the percent growth inhibition of the following organisms:
              Table 2                                                     
______________________________________                                    
Antimicrobial Activity of                                                 
8-Quinolinesulfonyl Chloride at 500 PPM                                   
______________________________________                                    
Organism          Percent Growth Inhibition                               
______________________________________                                    
S. aureus         0                                                       
E. coli           0                                                       
C. albicans       0                                                       
P. Str-10         0                                                       
S. typhosa        0                                                       
M. phlei          50                                                      
B. subtilis       0                                                       
C. pelliculosa    0                                                       
A. aerogenes      0                                                       
P. pullulans      0                                                       
C. ips            0                                                       
Trichoderm Sp. Madison P-42                                               
                  0                                                       
R. nigricans      0                                                       
______________________________________                                    

Claims (1)

What is claimed is:
1. The compound which is 8-quinolinesulfonyl bromide and which corresponds to the formula ##STR3##
US05/716,747 1976-08-23 1976-08-23 Quinolinesulfonyl compounds Expired - Lifetime US4061639A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/716,747 US4061639A (en) 1976-08-23 1976-08-23 Quinolinesulfonyl compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/716,747 US4061639A (en) 1976-08-23 1976-08-23 Quinolinesulfonyl compounds

Publications (1)

Publication Number Publication Date
US4061639A true US4061639A (en) 1977-12-06

Family

ID=24879270

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/716,747 Expired - Lifetime US4061639A (en) 1976-08-23 1976-08-23 Quinolinesulfonyl compounds

Country Status (1)

Country Link
US (1) US4061639A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5047540A (en) * 1987-12-17 1991-09-10 Shionogi & Co., Ltd. Lipid derivatives

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2830029A (en) * 1955-04-28 1958-04-08 American Cyanamid Co Preparation of cellular products containing organic sulfonyl azides and composition thereof
US3714206A (en) * 1968-12-02 1973-01-30 Gruenenthal Chemie Benzo-2,3,1-diazaborines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2830029A (en) * 1955-04-28 1958-04-08 American Cyanamid Co Preparation of cellular products containing organic sulfonyl azides and composition thereof
US3714206A (en) * 1968-12-02 1973-01-30 Gruenenthal Chemie Benzo-2,3,1-diazaborines

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
Albert et al., J. Chem. Soc. 2384 (1959). *
Buchmann et al., J. Prakt Chem., 16,152, (1962). *
Chemical Abstracts, vol. 82, No. 19, 125,260j, (5/12/75). *
Chivers, Aust. J. Chem., 1975, 28(2) 413-419, (1975). *
Claus et al., J. Prakt Chem. 40, 447, (1889). *
McCasland, J. Org. Chem., II, 277-280, (1946). *
Ponci et al., Chemical Abstracts, vol. 49, 11,657b, (1955). *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5047540A (en) * 1987-12-17 1991-09-10 Shionogi & Co., Ltd. Lipid derivatives

Similar Documents

Publication Publication Date Title
US3849420A (en) Bis-(alkylthio-and alkylsulfonyl)-pentachloroquinolines
US2802818A (en) Phthalides
US3734928A (en) Difunctional iodonium salts of diphenyl oxide and preparation
US4061639A (en) Quinolinesulfonyl compounds
US4053633A (en) Aryl dibromonitromethyl sulfones
US4048167A (en) N,N-disubstituted derivatives of 3-carboxamide or 3-thiocarboxamide-7-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane and preparation II
US3712920A (en) 2,5-thiophenediyl-bis(iodonium salts)
US4069341A (en) Oxybis(4,1-phenylene(2-oxo-2,1-ethanediyl)) thiocyanate and its use as an antimicrobial agent
US3940389A (en) 4 (3H)-Oxobenzo-2,1,3-thiadiazine-2,2-dioxides
US4210645A (en) (1,4)Dithiino(2,3-b)(1,2,5)-thiadiazole(3,4-e)pyrazine-6,7-dicarbonitrile
US2847473A (en) 2, 3-dichloro-nu-(omicron-chlorobenzylidene) aniline
US3850929A (en) (1,2,5)thiadiazolo(3,4-b)pyrazines
US3394145A (en) Nu-(3, 4-dichlorophenyl) maleimide
US4075205A (en) (1,3-Dithiolo-(4,5-b) (1,2,5)thiadiazolo(3',4'-e)pyrazin-6-ylidene)-propanedinitrile
US4094880A (en) Bis(chloromethylthio)thiadiazoles
US4193935A (en) Novel oxiodinium and thiaiodinium compounds
US2847472A (en) Condensation products of 2, 3-dichloroaniline and a benzaldehyde compound
US3303206A (en) Halogenated thiocyanato phenols
US4199581A (en) 1,4-Dithiino pyrazine tetracarbonitriles
US4150130A (en) 5,6-Dihydro-5-oxo-1,4-dithiino (2,3-d) pyridazine-2,3-dicarbonitriles
US3515726A (en) 2,2'-bis(pyridyl-n-oxide) dithiolcarbonates and trithiocarbonates
US3865822A (en) 1,1-Dihalo-1-(methylsulfonyl)methanesulfonamides
US4172133A (en) (1,4)Dithiino(2,3-b)(1,3)thiazole-(4,5-e)pyrazine-6,7-dicarbonitriles
US4101546A (en) Cyanatothiomethylthio pyrazines
US4147784A (en) 4,5-Dihydro-4-oxo-1,3-dithiolo(4,5-D)pyridazine-2-ylidene-propanedinitriles